High temperature ALD process of metal oxide for DRAM applications

ABSTRACT

A first electrode layer for a Metal-Insulator-Metal (MIM) DRAM capacitor is formed wherein the first electrode layer contains a conductive metal oxide formed using a high temperature, low pressure ALD process. The high temperature ALD process results in a layer with enhanced crystallinity, higher density, reduced shrinkage, and lower carbon contamination. The high temperature ALD process can be used for either or both the bottom electrode and the top electrode layers.

This document relates to the subject matter of a joint researchagreement between Intermolecular, Inc. and Elpida Memory, Inc

FIELD OF THE DISCLOSURE

The present disclosure relates generally to the use of non-noble metalelectrodes in capacitors used in Dynamic Random Access Memory (DRAM)devices.

BACKGROUND OF THE DISCLOSURE

Dynamic Random Access Memory utilizes capacitors to store bits ofinformation within an integrated circuit. A capacitor is formed byplacing a dielectric material between two electrodes formed fromconductive materials. A capacitor's ability to hold electrical charge(i.e., capacitance) is a function of the surface area of the capacitorplates A, the distance between the capacitor plates d (i.e. the physicalthickness of the dielectric layer), and the relative dielectric constantor k-value of the dielectric material. The capacitance is given by:

$\begin{matrix}{C = {\kappa\; ɛ_{o}\frac{A}{d}}} & \left( {{Eqn}.\mspace{14mu} 1} \right)\end{matrix}$where ∈_(o) represents the vacuum permittivity.

The dielectric constant is a measure of a material's polarizability.Therefore, the higher the dielectric constant of a material, the moreelectrical charge the capacitor can hold. Therefore, for a given desiredcapacitance, if the k-value of the dielectric is increased, the area ofthe capacitor can be decreased to maintain the same cell capacitance.Reducing the size of capacitors within the device is important for theminiaturization of integrated circuits. This allows the packing ofmillions (mega-bit (Mb)) or billions (giga-bit (Gb)) of memory cellsinto a single semiconductor device. The goal is to maintain a large cellcapacitance (generally ˜10 to 25 fF) and a low leakage current(generally <10⁻⁷ A cm⁻²). The physical thickness of the dielectriclayers in DRAM capacitors could not be reduced unlimitedly in order toavoid leakage current caused by tunneling mechanisms which exponentiallyincreases as the thickness of the dielectric layer decreases.

Traditionally, SiO₂ has been used as the dielectric material andsemiconducting materials (semiconductor-insulator-semiconductor [SIS]cell designs) have been used as the electrodes. The cell capacitance wasmaintained by increasing the area of the capacitor using very complexcapacitor morphologies while also decreasing the thickness of the SiO₂dielectric layer. Increases of the leakage current above the desiredspecifications have demanded the development of new capacitorgeometries, new electrode materials, and new dielectric materials. Celldesigns have migrated to metal-insulator-semiconductor (MIS) and now tometal-insulator-metal (MIM) cell designs for higher performance.

Typically, DRAM devices at technology nodes of 80 nm and below use MIMcapacitors wherein the electrode materials are metals. These electrodematerials generally have higher conductivities than the semiconductorelectrode materials, higher work functions, exhibit improved stabilityover the semiconductor electrode materials, and exhibit reduceddepletion effects. The electrode materials must have high conductivityto ensure fast device speeds. Representative examples of electrodematerials for MIM capacitors are metals, conductive metal oxides,conductive metal silicides, conductive metal nitrides (i.e. TiN), orcombinations thereof. MIM capacitors in these DRAM applications utilizeinsulating materials having a dielectric constant, or k-value,significantly higher than that of SiO₂ (k=3.9). For DRAM capacitors, thegoal is to utilize dielectric materials with k values greater than about20. Such materials are generally classified as high-k materials.Representative examples of high-k materials for MIM capacitors arenon-conducting metal oxides, non-conducting metal nitrides,non-conducting metal silicates or combinations thereof. Thesedielectrics may also include additional dopant materials.

One class of high-k dielectric materials possessing the characteristicsrequired for implementation in advanced DRAM capacitors are high-k metaloxide materials. Titanium oxide is a metal oxide dielectric materialwhich displays significant promise in terms of serving as a high-kdielectric material for implementation in DRAM capacitors.

The dielectric constant of a dielectric material may be dependent uponthe crystalline phase(s) of the material. For example, in the case oftitanium oxide, the anatase crystalline phase of titanium oxide has adielectric constant of approximately 40, while the rutile crystallinephase of titanium oxide can have a dielectric constant ofapproximately >80. Due to the higher-k value of the rutile-phase, it isdesirable to produce titanium oxide based DRAM capacitors with thetitanium oxide in the rutile-phase. The relative amounts of the anatasephase and the rutile phase can be determined from x-ray diffraction(XRD). From Eqn. 1 above, a titanium oxide layer in the rutile-phasecould be physically thicker and maintain the desired capacitance. Theincreased physical thickness is important for lowering the leakagecurrent of the capacitor. The anatase phase will transition to therutile phase at high temperatures (>800 C). However, high temperatureprocesses are undesirable in the manufacture of DRAM devices.

The crystal phase of an underlying layer can be used to influence thegrowth of a specific crystal phase of a subsequent material if theircrystal structures are similar and their lattice constants are similar.This technique is well known in technologies such as epitaxial growth.The same concepts have been extended to the growth of thin films wherethe underlying layer can be used as a “template” to encourage the growthof a desired phase over other competing crystal phases.

Conductive metal oxides, conductive metal silicides, conductive metalnitrides, conductive metal carbides, or combinations thereof areexamples of other classes of materials that may be suitable as DRAMcapacitor electrodes. Generally, transition metals and their conductivebinary compounds form good candidates as electrode materials. Thetransition metals exist in several oxidation states. Therefore, a widevariety of compounds are possible. Different compounds may havedifferent crystal structures, electrical properties, etc. It isimportant to utilize the proper compound for the desired application.

In one example, molybdenum has several binary oxides of which MoO₂ andMoO₃ are two examples. These two oxides of molybdenum have differentproperties. MoO₂ has shown great promise as an electrode material inDRAM capacitors. MoO₂ has a distorted rutile crystal structure andserves as an acceptable template to promote the deposition of therutile-phase of TiO₂ as discussed above. MoO₂ also has a high workfunction (can be >5.0 eV depending on process history) which helps tominimize the leakage current of the DRAM device. However, oxygen-richphases (MoO_(2+x)) degrade the performance of the MoO₂ electrode becausethey do not promote the deposition of the rutile-phase of TiO₂. Forexample, MoO₃ (the most oxygen-rich phase) has an orthorhombic crystalstructure.

Generally, a deposited thin film may be amorphous, crystalline, or amixture thereof. Furthermore, several different crystalline phases mayexist. Therefore, processes (both deposition and post-treatment) must bedeveloped to maximize the formation of crystalline MoO₂ and to minimizethe presence of MoO_(2+x) phases. Deposition processes andpost-treatment processes in a reducing atmosphere have been developedthat allow crystalline MoO₂ to be used as the first electrode (i.e.bottom electrode) in MIM DRAM capacitors with titanium oxide ordoped-titanium oxide high-k dielectric materials. Examples of thepost-treatment process are further described in U.S. application Ser.No. 13/084,666 filed on Apr. 12, 2011, entitled “METHOD FOR FABRICATINGA DRAM CAPACITOR” which is incorporated herein by reference. Otherconductive metal oxides that may be used as a template for the rutilephase of titanium oxide include the conductive compounds of molybdenumoxide, tungsten oxide, ruthenium oxide, iron oxide, iridium oxide,chromium oxide, manganese oxide, tin oxide, cobalt oxide, or nickeloxide.

As used herein, the phrase “conductive metal oxide” will be understoodto include the typical stoichiometric metal oxides as well as conductivenon-stoichiometric metal oxides wherein the oxygen to metal ratio is notequal to the stoichiometric ratio. As an example, “conductive molybdenumoxide” will include MoO₂ as well as those conductive molybdenum oxideswherein the oxygen to metal ratio is slightly greater than or slightlyless than 2. Those skilled in the art will understand that metal-oxygencompounds that are slightly off of the stoichiometric ratio will also beconductive and will fall within the scope of the present disclosure. Asused herein, the phrase “conductive metal oxide” will be understood toinclude metal oxide materials having a resistivity of less than about 10Ωcm.

The use of conductive metal oxide as an electrode layer (e.g. firstelectrode and/or second electrode) has a number of additional issues.The layers exhibit high shrinkage during subsequent annealingtreatments. The layers exhibit high surface roughness when deposited athigher temperatures. The layers can contain high levels of carboncontamination.

Therefore, there is a need to develop processes that allow the formationof a conductive metal oxide electrode layers (e.g. first electrodeand/or second electrode) that can serve as a template for the rutilephase of titanium oxide (e.g. first electrode embodiments), has a lowshrinkage, has low surface roughness, and has low carbon contamination.

SUMMARY OF THE DISCLOSURE

In some embodiments, a conductive metal oxide first electrode layer isformed as part of a MIM DRAM capacitor stack. In some embodiments, aconductive metal oxide layer is formed as part of a bilayer firstelectrode of a MIM DRAM capacitor stack. The conductive metal oxidefirst electrode layer is formed using a high temperature ALD process atlow pressure.

In some embodiments, a conductive metal oxide second electrode layer isformed as part of a MIM DRAM capacitor stack. In some embodiments, aconductive metal oxide layer is formed as part of a bilayer secondelectrode of a MIM DRAM capacitor stack. The conductive metal oxidesecond electrode layer is formed using a high temperature ALD process atlow pressure.

BRIEF DESCRIPTION OF THE DRAWINGS

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures. The drawings are not to scale and the relative dimensionsof various elements in the drawings are depicted schematically and notnecessarily to scale.

The techniques of the present disclosure can readily be understood byconsidering the following derailed description in conjunction with theaccompanying drawings, in which:

FIG. 1 presents data for deposition rate versus temperature at twodifferent pressures.

FIG. 2 presents a chart illustrating issues encountered in thepressure-temperature ALD process space and highlighting the region wherefilms with acceptable quality may be produced.

FIG. 3 illustrates a flow chart illustrating a method for fabricating aDRAM capacitor stack in accordance with some embodiments.

FIG. 4 illustrates a flow chart illustrating a method for fabricating aDRAM capacitor stack in accordance with some embodiments.

FIG. 5 illustrates a flow chart illustrating a method for fabricating aDRAM capacitor stack in accordance with some embodiments.

FIG. 6 illustrates a simplified cross-sectional view of a DRAM capacitorstack fabricated in accordance with some embodiments.

FIG. 7 illustrates a simplified cross-sectional view of a DRAM capacitorstack fabricated in accordance with some embodiments.

FIG. 8 illustrates a simplified cross-sectional view of a DRAM capacitorstack fabricated in accordance with some embodiments.

FIG. 9 illustrates a simplified cross-sectional view of a DRAM capacitorstack fabricated in accordance with some embodiments.

FIG. 10 illustrates a simplified cross-sectional view of a DRAM memorycell fabricated in accordance with some embodiments.

DETAILED DESCRIPTION

A detailed description of one or more embodiments is provided belowalong with accompanying figures. The detailed description is provided inconnection with such embodiments, but is not limited to any particularexample. The scope is limited only by the claims and numerousalternatives, modifications, and equivalents are encompassed. Numerousspecific details are set forth in the following description in order toprovide a thorough understanding. These details are provided for thepurpose of example and the described techniques may be practicedaccording to the claims without some or all of these specific details.For the purpose of clarity, technical material that is known in thetechnical fields related to the embodiments has not been described indetail to avoid unnecessarily obscuring the description.

It must be noted that as used herein and in the claims, the singularforms “a,” “and” and “the” include plural referents unless the contextdearly dictates otherwise. Thus, for example, reference to “a layer”also includes two or more layers, and so forth. As an example, thoseskilled in the art will understand that an “electrode layer” may includea single layer or may include a “bilayer” of two materials.

As discussed previously, it is possible to implement a conductive metaloxide as the first electrode layer in a DRAM capacitor stack. Conductivemetal oxide materials of interest are able to serve as a template andpromote the high k crystalline phases of metal oxide dielectricmaterials formed on the surface of these metal oxide materials. Someconductive metal oxide materials can promote the high k rutile phase oftitanium oxide. Examples of such conductive metal oxides include theconductive compounds of molybdenum oxide, tungsten oxide, rutheniumoxide, iridium oxide, chromium oxide, manganese oxide, or tin oxide.Specific conductive metal oxide materials of interest are the conductivemetal compounds of molybdenum oxide, ruthenium oxide, manganese oxide,tungsten oxide, and tin oxide. Typically, conductive metal oxidematerials are deposited using atomic layer deposition (ALD) processes.Exemplary conductive metal oxide ALD precursors include alkyls,alkylamides, aryls, alkoxides, carbonyls, b-diketonates,cyclopentadienyls, amines, amido complexes, amidinates, halides, and thelike. ALD processes were evaluated at temperatures between about 180 Cand about 240 C and at pressures of about 2.5 torr. At thesetemperatures and pressures, the deposition rate was typically betweenabout 0.5 A/cycle and about 2.0 A/cycle. However, conductive metal oxidematerials formed from ALD processes using these process parametersgenerally exhibited low density, high shrinkage after annealing, highsurface roughness, and higher carbon contamination.

To address the issues discussed previously, the temperature of the ALDdeposition can be increased. This results in conductive metal oxidelayers which exhibit higher density and lower shrinkage after annealing.However, since the metal organic precursors do not exhibit perfect ALDbehavior (e.g. they are not truly self-limiting), there is a chemicalvapor deposition (CVD) component to the deposition that can be observedat higher temperatures. The influence of the CVD component to thedeposition can be decreased by lowering the pressure during thedeposition. The magnitude of the CVD component will decrease withlowering pressure while the ALD component will be unaffected. Thedeposition of conductive molybdenum oxide will be used as an example.The data presented herein was obtained using a metal organic molybdenumprecursor wherein the molybdenum was present in the +4 valence state.The data obtained were better than those obtained using metal organicmolybdenum precursors wherein the molybdenum was present in either the+2 or +6 valence states. Those skilled in the art will understand thatthis can be extended to the deposition of the other conductive metaloxides listed previously. This is illustrated in FIG. 1 wherein thedeposition rate of conductive molybdenum oxide increases from about 2.5A/cycle at a temperature of 240 C and a pressure of 2.5 Torr to about7.0 A/cycle at a temperature of 360 C and a pressure of 2.5 Torr. Incontrast, the deposition rate of conductive molybdenum oxide increasesfrom about 1.8 A/cycle at a temperature of 260 C and a pressure of 0.25Torr to about 3.0 A/cycle at a temperature of 360 C and a pressure of0.25 Torr. The lower pressure has allowed the CVD component of thedeposition to be suppressed.

The conductive molybdenum oxide layers deposited at 360 C and 0.25 Torrpressure exhibit smooth surface roughness. For example, in someembodiments, a surface roughness of about 10 A was measured for aconductive molybdenum oxide layer with a thickness of about 10 nm formedon a titanium nitride base layer (i.e. a bilayer electrode layer). Thislevel of surface roughness for the first electrode layer is acceptablefor advanced DRAM capacitor stacks.

The conductive molybdenum oxide layers deposited at 360 C and 0.25 Torrpressure exhibit reduced shrinkage after an anneal process. For example,in some embodiments, conductive molybdenum oxide layers deposited at 180C and 2.5 Torr pressure exhibited a shrinkage of about 35% after ananneal process to crystallize the layer. The crystallization annealprocess was at a temperature of about 450 C Conductive molybdenum oxidelayers deposited at 240 C and 2.5 Torr pressure exhibited a shrinkage ofabout 15% after an anneal process to crystallize the layer. Conductivemolybdenum oxide layers deposited at 360 C and 0.25 Torr pressureexhibited a shrinkage of about 7% after an anneal process to crystallizethe layer. FIG. 2 presents a chart illustrating issues encountered inthe pressure-temperature ALD process space and highlighting the regionwhere films with acceptable quality may be produced. At pressuresgreater than about 1.0 Torr, the films exhibit high roughness and maybecome discontinuous. At pressures greater than 1.0 Torr, the highroughness increased as the deposition temperature increased, leading tovery high roughness at temperatures above about 360 C At pressures belowabout 0.1 Torr, issues with precursor supply and pressure stability wereencountered. Films deposited at the lower temperatures (i.e. <˜280 C)may exhibit poor crystallization, high shrinkage, and highercontamination. Films deposited at the higher temperatures (i.e. >˜360 C)may exhibit very high roughness and issues with film discontinuity wereencountered. Therefore, the beneficial range is believed to be betweenabout 0.1 Torr and 1.0 Torr in pressure and between about 280 C and 360C in temperature. Films deposited in this range were smooth, continuous,exhibited low shrinkage, and exhibited low contamination. This dataclearly indicate the benefits of the higher temperature and lowerpressure deposition. After the crystallization anneal process,transmission electron microscopy (TEM) verified that the conductivemolybdenum oxide layers were continuous, with no voids.

The goal of the crystallization anneal process is to convert a portion(e.g. more than 30% as measured by XRD) of the conductive molybdenumoxide layers to crystalline molybdenum oxide. As discussed previously,crystalline molybdenum oxide has a distorted rutile crystal structureand is effective at promoting the growth of the high k phase ofdielectric materials such as the rutile phase of titanium oxide. Thegrowth of rutile phase titanium oxide on crystallized molybdenum oxidedeposited at a temperature of 360 C and at a pressure of 0.25 Torr hasbeen confirmed.

Capacitor stacks were formed to test the performance of the molybdenumoxide layers deposited at a temperature of 360 C and at a pressure of0.25 Torr as part of the first electrode structure. The capacitor stacksincluded a titanium nitride base layer (i.e. a bilayer electrode layer),a conductive molybdenum oxide layer as part of the first electrodelayer, a titanium oxide dielectric layer doped with aluminum, and aplatinum second electrode layer. Capacitor stacks were formed whereinthe conductive molybdenum oxide layer was formed at 240 C, 280 C, or 360C All capacitor stacks were formed at a pressure in the range of about0.25 Torr to about 0.50 Torr. Table 1 presents data that compares themeasured EOT values and the leakage current density for the variouscapacitor stacks. The data indicate that low values of EOT and theleakage current density (e.g. both are evidence of a high k value of thedielectric layer) can be obtained using a high temperature, low pressuredeposition for the conductive molybdenum oxide portion of the firstelectrode layer.

TABLE 1 Conductive molybdenum oxide deposition J at 1.0 V temperature(C.) EOT (nm) (A/cm²) 240 0.65  2.4E−7 280 0.60 3.00E−7 360 0.60 1.03E−7

In addition to the issues regarding the CVD component of the depositionat higher temperatures discussed previously, the reactivity of thereactant is also much more aggressive at higher deposition temperatures.Typically, ozone is used as a reactant for the deposition of metaloxides, used either as electrode layers or as dielectric layers.However, other reactants, such as water or oxygen, are also commonlyused. When ozone is used as the reactant, concentrations between about3% and about 20% are typical. However, at higher temperatures, such as360 C, the higher concentrations of ozone are too aggressive and reactwith the precursor to form oxygen-rich metal oxide compounds (e.g. theyform MoO_(2+x) or MoO₃ in the case of molybdenum), As discussedpreviously, these compounds are undesirable. Additionally, the higherconcentrations of ozone may react with the underlying titanium nitrideto form titanium oxy-nitride compounds that degrade the performance ofthe first electrode structure and lead to increased leakage current.

To address these issues, ozone concentrations as low as 1% were employedto form the conductive metal oxide layer. Conductive molybdenum oxidewill be used as an example. Capacitor stacks were formed to test theperformance of the molybdenum oxide layers deposited at a temperature of360 C, a pressure of 0.25 Torr, and an ozone concentration of 1% as partof the first electrode layer. The capacitor stacks included a titaniumnitride base layer, a conductive molybdenum oxide layer as part of thefirst electrode layer, a titanium oxide dielectric layer doped withaluminum, and a platinum second electrode layer. Capacitor stacks wereformed wherein the conductive molybdenum oxide layer was formed at apressure in the range of about 0.25 Torr to about 0.50 Torr. The ozonepulse was varied from 30 seconds to 90 seconds to test the sensitivityof the device performance to the ozone pulse time. Table 2 presents datathat compares the measured EOT values and the leakage current densityfor the various capacitor stacks. The data indicate that low values ofEOT and the leakage current density (e.g. both are evidence of a high kvalue of the dielectric layer) can be obtained using a high temperature,low pressure deposition for the conductive molybdenum oxide portion ofthe first electrode layer over a wide range of ozone pulse times.

TABLE 2 Ozone pulse time J at 1.0 V (sec) EOT (nm) (A/cm²) K-value 300.63 9.70E−8 49.0 45 0.61 2.69E−7 50.5 60 0.59 1.16E−7 51.9 90 0.611.10E−7 50.9

FIG. 3 describes a method, 300, for fabricating a DRAM capacitor stack.The initial step, 302, includes forming a first electrode layer above asubstrate. Examples of suitable electrode materials include metals,conductive metal oxides, conductive metal silicides, conductive metalnitrides, and combinations thereof. A particularly interesting class ofmaterials is the conductive metal oxides. The first electrode is formedusing a high temperature, low pressure atomic layer deposition (ALD)process. The first electrode layer can then be subjected to an annealingprocess (not shown). The first electrode layer may include a singlelayer or may include multiple layers as discussed previously. The nextstep, 304, includes forming a dielectric layer above the first electrodelayer. Optionally, the dielectric layer can then be subjected to a postdielectric anneal (PDA) treatment (not shown). The PDA step serves tocrystallize the dielectric layer and fill oxygen vacancies. The nextstep, 306, includes forming a second electrode layer on the dielectriclayer. The second electrode layer may include a single layer or mayinclude multiple layers as discussed previously. Examples of suitableelectrode materials include metals, conductive metal oxides, conductivemetal silicides, conductive metal nitrides, and combinations thereof.Optionally, the capacitor stack can then be subjected to PMA treatmentprocess in an oxidizing atmosphere, wherein the oxidizing atmosphereincludes between 0% O₂ to 20% O₂ and at temperatures between 300 C to600 C for between 1 millisecond to 60 minutes (not shown). Examples ofthe PDA and PMA treatments are further described in U.S. applicationSer. No. 13/159,842 filed on Jun. 14, 2011, entitled “METHOD OFPROCESSING MIM CAPACITORS TO REDUCE LEAKAGE CURRENT” and is incorporatedherein by reference for all purposes. Those skilled in the art willunderstand that other layers may be included in the capacitor stack.

FIG. 4 describes a method, 400, for fabricating a DRAM capacitor stack.The initial step, 402, includes forming a first electrode layer above asubstrate. The first electrode layer may include a single layer or mayinclude multiple layers as discussed previously. The next step, 404,includes forming a dielectric layer above the first electrode layer.Optionally, the dielectric layer can then be subjected to a PDAtreatment (not shown). The PDA step serves to crystallize the dielectriclayer and fill oxygen vacancies. The next step, 406, includes forming asecond electrode layer above the dielectric layer. The second electrodelayer may include a single layer or may include multiple layers asdiscussed previously. Examples of suitable second electrode materialsinclude metals, conductive metal oxides, conductive metal silicides,conductive metal nitrides, and combinations thereof. A particularlyinteresting class of materials is the conductive metal oxides. Thesecond electrode layer is formed using a high temperature, low pressureALD process. Optionally, the capacitor stack can then be subjected toPMA treatment process in an oxidizing atmosphere, wherein the oxidizingatmosphere includes between 0% O₂ to 20% O₂ and at temperatures between300 C to 600 C for between 1 millisecond to 60 minutes (not shown).Those skilled in the art will understand that other layers may beincluded in the capacitor stack.

FIG. 5 describes a method, 500, for fabricating a DRAM capacitor stack.The initial step, 502, includes forming a first electrode layer above asubstrate. The first electrode layer may include a single layer or mayinclude multiple layers as discussed previously. Examples of suitableelectrode materials include metals, conductive metal oxides, conductivemetal silicides, conductive metal nitrides, and combinations thereof. Aparticularly interesting class of materials is the conductive metaloxides. The first electrode layer is formed using a high temperature,low pressure ALD process. The first electrode layer can then besubjected to an annealing process (not shown). The next step, 504,includes forming a dielectric layer above the first electrode layer.Optionally, the dielectric layer can then be subjected to a PDAtreatment (not shown). The PDA step serves to crystallize the dielectriclayer and fill oxygen vacancies. The next step, 506, includes forming asecond electrode layer above the dielectric layer. The second electrodelayer may include a single layer or may include multiple layers asdiscussed previously. Examples of suitable second electrode materialsinclude metals, conductive metal oxides, conductive metal silicides,conductive metal nitrides, and combinations thereof. A particularlyinteresting class of materials is the conductive metal oxides. Thesecond electrode layer is formed using a high temperature, low pressureALD process. Optionally, the capacitor stack can then be subjected toPMA treatment process in an oxidizing atmosphere, wherein the oxidizingatmosphere includes between 0% O₂ to 20% O₂ and at temperatures between300 C to 600 C for between 1 millisecond to 60 minutes (not shown).Those skilled in the art will understand that other layers may beincluded in the capacitor stack.

Those skilled in the art will appreciate that the formation of each ofthe first electrode layer, the dielectric layer, and the secondelectrode structure used in the MIM DRAM capacitor has been describedusing a generic ALD process. However, any of the variants of the genericALD process may also be implemented. Common variants include plasmaenhanced atomic layer deposition (PE-ALD), atomic vapor deposition(AVD), and ultraviolet assisted atomic layer deposition (UV-ALD), etc.Generally, because of the complex morphology of the DRAM capacitorstructure, ALD, PE-ALD, AVD, or UV-ALD are preferred methods offormation. However, any of these techniques are suitable for formingeach of the various layers discussed herein. Those skilled in the artwill appreciate that the teachings described herein are not limited bythe variant of the ALD technology used for the deposition process.

In FIGS. 6-10 below, a capacitor stack is illustrated using a simpleplanar structure. Those skilled in the art will appreciate that thedescription and teachings to follow can be readily applied to any simpleor complex capacitor morphology. The drawings are for illustrativepurposes only and do not limit the application of the present invention.

FIG. 6 illustrates a simple capacitor stack, 600, consistent with someembodiments. Using the method as outlined in FIG. 3 and describedpreviously, first electrode layer, 602, is formed above substrate, 601.Generally, the substrate has already received several processing stepsin the manufacture of a full DRAM device. First electrode layer, 602,includes one of metals, conductive metal oxides, conductive metalnitrides, conductive metal silicides, etc. The first electrode layer mayinclude a single layer or may include multiple layers as discussedpreviously. In some embodiments, the first electrode layer includes aconductive metal oxide. The conductive metal oxide portion of the firstelectrode is formed using a high temperature, low pressure ALD processas discussed previously. In some embodiments, the first electrode layermay include at least one of the conductive compounds of molybdenumoxide, tungsten oxide, ruthenium oxide, iridium oxide, chromium oxide,manganese oxide, or tin oxide. Specific conductive metal oxide materialsof interest are the conductive metal compounds of molybdenum oxide,ruthenium oxide, manganese oxide, tungsten oxide, and tin oxide. In someembodiments, the first electrode layer includes a conductive base layerformed under the conductive metal oxide. In some embodiments, theconductive base layer includes one of ruthenium, platinum, titaniumnitride, tantalum nitride, titanium-aluminum-nitride, tungsten, tungstennitride, molybdenum, molybdenum nitride, or vanadium nitride. The firstelectrode layer, 602, can be annealed to crystallize the material.

In the next step, dielectric layer, 604, would then be formed above thefirst electrode layer, 602. A wide variety of dielectric materials havebeen targeted for use in DRAM capacitors. Examples of suitabledielectric materials include aluminum oxide, barium-strontium-titanate(BST), hafnium oxide, hafnium silicate, niobium oxide,lead-zirconium-titanate (PZT), a bilayer of silicon oxide and siliconnitride, silicon oxy-nitride, strontium-titanate (STO), tantalum oxide,titanium oxide, zirconium oxide or doped versions of the same. As usedherein, a “dopant” is a minor constituent (generally <20 atomic %) of alayer or material that is purposely added. As used herein, the dopantmay be electrically active or not electrically active. The definitionexcludes residues and impurities such as carbon, etc. that may bepresent in the material due to inefficiencies of the process orimpurities in the precursor materials. These dielectric materials may beformed as a single layer or may be formed as a hybrid or nanolaminatestructure. In some embodiments, the dielectric layer is doped TiO₂.Typical dopants for titanium oxide include Al, Ce, Co, Er, Ga, Gd, Ge,Hf, In, La, Lu, Mg, Mn, Nd, Pr, Sc, Si, Sn, Sr, Y, Zr, or combinationsthereof. Typically, dielectric layer, 604, is subjected to a PDAtreatment before the formation of the second electrode layer asdiscussed previously.

In the next step, the second electrode layer, 606, is formed abovedielectric layer, 604. The second electrode layer includes one ofmetals, conductive metal oxides, conductive metal nitrides, conductivemetal silicides, conductive metal carbides, etc. Typically, thecapacitor stack would then be subjected to a PMA treatment in anoxidizing atmosphere, wherein the oxidizing atmosphere includes between0% O₂ to 20% O₂ and at temperatures between 300 C to 600 C for between 1millisecond to 60 minutes. Those skilled in the art will understand thatother layers may be included in the capacitor stack.

FIG. 7 illustrates a simple capacitor stack, 700, consistent with someembodiments. Using the method as outlined in FIG. 4 and described above,first electrode layer, 702, is formed above substrate, 701. Generally,the substrate has already received several processing steps in themanufacture of a full DRAM device. First electrode layer, 702, includesone of metals, conductive metal oxides, conductive metal nitrides,conductive metal silicides, etc. The first electrode layer may include asingle layer or may include multiple layers as discussed previously. Insome embodiments, the conductive metal oxide portion of the firstelectrode layer is a conductive metal oxide. In some embodiments, thefirst electrode layer may include at least one of the conductivecompounds of molybdenum oxide, tungsten oxide, ruthenium oxide, iridiumoxide, chromium oxide, manganese oxide, or tin oxide. Specificconductive metal oxide materials of interest are the conductive metalcompounds of molybdenum oxide, ruthenium oxide, manganese oxide,tungsten oxide, and tin oxide. In some embodiments, the first electrodelayer includes a conductive base layer formed under the conductive metaloxide. In some embodiments, the conductive base layer includes one ofruthenium, platinum, titanium nitride, tantalum nitride,titanium-aluminum-nitride, tungsten, tungsten nitride, molybdenum,molybdenum nitride, or vanadium nitride. The first electrode layer, 702,can be annealed to crystallize the material.

In the next step, dielectric layer, 704, would then be formed above thefirst electrode layer, 702. A wide variety of dielectric materials havebeen targeted for use in DRAM capacitors. Examples of suitabledielectric materials include aluminum oxide, barium-strontium-titanate(BST), hafnium oxide, hafnium silicate, niobium oxide,lead-zirconium-titanate (PZT), a bilayer of silicon oxide and siliconnitride, silicon oxy-nitride, strontium-titanate (STO), tantalum oxide,titanium oxide, zirconium oxide or doped versions of the same. Thesedielectric materials may be formed as a single layer or may be formed asa hybrid or nanolaminate structure. In some embodiments, the dielectriclayer is doped titanium oxide. Typical dopants for titanium oxideinclude Al, Ce, Co, Er, Ga, Gd, Ge, Hf, In, La, Lu, Mg, Mn, Nd, Pr, Sc,Si, Sn, Sr, Y, Zr, or combinations thereof. Typically, dielectric layer,704, is subjected to a PDA treatment before the formation of the secondelectrode layer as discussed previously.

In the next step, the second electrode layer, 706, is formed abovedielectric layer, 704. The second electrode layer includes one ofmetals, conductive metal oxides, conductive metal nitrides, conductivemetal silicides, conductive metal carbides, etc. The second electrodelayer may include a single layer or may include multiple layers asdiscussed previously. In some embodiments, the conductive metal oxideportion of the second electrode layer is a conductive metal oxide. Insome embodiments, the second electrode layer may include at least one ofthe conductive compounds of molybdenum oxide, tungsten oxide, rutheniumoxide, iridium oxide, chromium oxide, manganese oxide, or tin oxide.Specific conductive metal oxide materials of interest are the conductivemetal compounds of molybdenum oxide, ruthenium oxide, manganese oxide,tungsten oxide, and tin oxide. In some embodiments, the second electrodelayer includes a conductive base layer formed above the conductive metaloxide. In some embodiments, the conductive base layer includes one ofruthenium, platinum, titanium nitride, tantalum nitride,titanium-aluminum-nitride, tungsten, tungsten nitride, molybdenum,molybdenum nitride, or vanadium nitride. The conductive metal oxideportion of the second electrode is formed using a high temperature, lowpressure ALD process as discussed previously. Typically, the capacitorstack would then be subjected to a PMA treatment in an oxidizingatmosphere, wherein the oxidizing atmosphere includes between 0% O₂ to20% O₂ and at temperatures between 300 C to 600 C for between 1millisecond to 60 minutes. Those skilled in the art will understand thatother layers may be included in the capacitor stack.

FIG. 8 illustrates a simple capacitor stack, 800, consistent with someembodiments. Using the method as outlined in FIG. 5 and described above,first electrode layer, 802, is formed above substrate, 801. Generally,the substrate has already received several processing steps in themanufacture of a full DRAM device. First electrode layer, 802, includesone of metals, conductive metal oxides, conductive metal nitrides,conductive metal silicides, etc. The first electrode layer may include asingle layer or may include multiple layers as discussed previously. Insome embodiments, the first electrode layer includes a conductive metaloxide. The conductive metal oxide portion of the first electrode isformed using a high temperature, low pressure ALD process as discussedpreviously. In some embodiments, the first electrode layer may includeat least one of the conductive compounds of molybdenum oxide, tungstenoxide, ruthenium oxide, iridium oxide, chromium oxide, manganese oxide,or tin oxide. Specific conductive metal oxide materials of interest arethe conductive metal compounds of molybdenum oxide, ruthenium oxide,manganese oxide, tungsten oxide, and tin oxide. In some embodiments, thefirst electrode layer includes a conductive base layer formed under theconductive metal oxide. In some embodiments, the conductive base layerincludes one of ruthenium, platinum, titanium nitride, tantalum nitride,titanium-aluminum-nitride, tungsten, tungsten nitride, molybdenum,molybdenum nitride, or vanadium nitride. The first electrode, 802, canbe annealed to crystallize the material.

In the next step, dielectric layer, 804, would then be formed above thefirst electrode layer, 802. A wide variety of dielectric materials havebeen targeted for use in DRAM capacitors. Examples of suitabledielectric materials include aluminum oxide, barium-strontium-titanate(BST), hafnium oxide, hafnium silicate, niobium oxide,lead-zirconium-titanate (PZT), a bilayer of silicon oxide and siliconnitride, silicon oxy-nitride, strontium-titanate (STO), tantalum oxide,titanium oxide, zirconium oxide or doped versions of the same. Thesedielectric materials may be formed as a single layer or may be formed asa hybrid or nanolaminate structure. In some embodiments, the dielectriclayer is doped titanium oxide. Typical dopants for titanium oxideinclude Al, Ce, Co, Er, Ga, Gd, Ge, Hf, In, La, Lu, Mg, Mn, Nd, Pr, Sc,Si, Sn, Sr, Y, Zr, or combinations thereof. Typically, dielectric layer,804, is subjected to a PDA treatment before the formation of the secondelectrode layer as discussed previously.

In the next step, the second electrode layer, 806, is formed abovedielectric layer, 804. The second electrode layer includes one ofmetals, conductive metal oxides, conductive metal nitrides, conductivemetal silicides, conductive metal carbides, etc. The second electrodelayer may include a single layer or may include multiple layers asdiscussed previously. In some embodiments, the conductive metal oxideportion of the second electrode layer is a conductive metal oxide. Insome embodiments, the second electrode layer may include at least one ofthe conductive compounds of molybdenum oxide, tungsten oxide, rutheniumoxide, iridium oxide, chromium oxide, manganese oxide, or tin oxide.Specific conductive metal oxide materials of interest are the conductivemetal compounds of molybdenum oxide, ruthenium oxide, manganese oxide,tungsten oxide, and tin oxide. In some embodiments, the second electrodelayer includes a conductive base layer formed above the conductive metaloxide. In some embodiments, the conductive base layer includes one ofruthenium, platinum, titanium nitride, tantalum nitride,titanium-aluminum-nitride, tungsten, tungsten nitride, molybdenum,molybdenum nitride, or vanadium nitride. The conductive metal oxideportion of the second electrode is formed using a high temperature, lowpressure ALD process as discussed previously. Typically, the capacitorstack would then be subjected to a PMA treatment in an oxidizingatmosphere, wherein the oxidizing atmosphere includes between 0% O₂ to20% O₂ and at temperatures between 300 C to 600 C for between 1millisecond to 60 minutes. Those skilled in the art will understand thatother layers may be included in the capacitor stack.

FIG. 9 illustrates a simple capacitor stack, 900, consistent with someembodiments. Using the method as outlined in FIG. 3 and described above,first electrode layer, 902, is formed above substrate, 901. Generally,the substrate has already received several processing steps in themanufacture of a full DRAM device. First electrode layer, 902, includesone of metals, conductive metal oxides, conductive metal nitrides,conductive metal silicides, conductive metal carbides, etc. For thisexample, first electrode layer, 902, includes a conductive metal oxidethat may serve to promote the rutile phase of titanium oxide. The firstelectrode layer may include a single layer or may include multiplelayers as discussed previously. In some embodiments, the first electrodelayer includes a conductive metal oxide. The conductive metal oxideportion of the first electrode is formed using a high temperature, lowpressure ALD process as discussed previously. In some embodiments, thefirst electrode layer may include at least one of the conductivecompounds of molybdenum oxide, tungsten oxide, ruthenium oxide, iridiumoxide, chromium oxide, manganese oxide, or tin oxide. Specificconductive metal oxide materials of interest are the conductive metalcompounds of molybdenum oxide, ruthenium oxide, manganese oxide,tungsten oxide, and tin oxide. In some embodiments, the first electrodelayer includes a conductive base layer formed under the conductive metaloxide. In some embodiments, the conductive base layer includes one ofruthenium, platinum, titanium nitride, tantalum nitride,titanium-aluminum-nitride, tungsten, tungsten nitride, molybdenum,molybdenum nitride, or vanadium nitride.

Optionally, first electrode, 902, can be annealed to crystallize thematerial. In the case of crystalline conductive molybdenum oxide, it isadvantageous to anneal the first electrode layer in a reducingatmosphere to prevent the formation of oxygen-rich compounds asdiscussed previously.

In some embodiments, a first electrode layer including between about 5nm and about 15 nm of conductive molybdenum oxide is formed on asubstrate (or on a titanium nitride base layer). The conductivemolybdenum oxide electrode layer is formed at a process temperaturebetween about 280 C and about 360 C and a pressure between about 0.10Torr and about 1.00 Torr using an ALD process technology. Optionally,the substrate with the first electrode layer is then annealed in areducing atmosphere including between about 0% and about 10% H₂ in N₂ orother inert gases and advantageously between about 5% and about 10% H₂in N₂ or other inert gases between about 400 C and about 650 C forbetween about 1 millisecond and about 60 minutes.

In the next step, dielectric layer, 904, would then be formed above thefirst electrode layer, 902. A wide variety of dielectric materials havebeen targeted for use in DRAM capacitors. Examples of suitabledielectric materials include aluminum oxide, barium-strontium-titanate(BST), hafnium oxide, hafnium silicate, niobium oxide,lead-zirconium-titanate (PZT), a bilayer of silicon oxide and siliconnitride, silicon oxy-nitride, strontium-titanate (STO), tantalum oxide,titanium oxide, zirconium oxide or doped versions of the same. Thesedielectric materials may be formed as a single layer or may be formed asa hybrid or nanolaminate structure. Typically, dielectric layer, 904, issubjected to a PDA treatment before the formation of the secondelectrode as discussed previously. In some embodiments, the dielectriclayer is doped titanium oxide. Typical dopants for titanium oxideinclude Al, Ce, Co, Er, Ga, Gd, Ge, Hf, In, La, Lu, Mg, Mn, Nd, Pr, Sc,Si, Sn, Sr, Y, Zr, or combinations thereof. A dielectric material ofinterest is TiO₂ doped with Al to between about 5 atomic % and about 15atomic % Al. The rutile phase of TiO₂ will form preferentially on theunderlying conductive molybdenum oxide electrode layer resulting in ahigher k value.

In some embodiments, the dielectric layer includes between about 6 nm toabout 10 nm of titanium oxide wherein at least 30% of the titanium oxideis present in the rutile phase. Generally, the titanium oxide dielectriclayer may either be a single film or may include a nanolaminate.Advantageously, the titanium oxide material is doped with Al at aconcentration between about 5 atomic % and about 15 atomic %. Thetitanium oxide dielectric layer is formed at a process temperaturebetween about 200 C and 350 C using an ALD process technology. Thesubstrate with the first electrode layer and dielectric layer is thenannealed in an oxidizing atmosphere including between about 0% O₂ toabout 100% O₂ in N₂ and advantageously between about 0% O₂ to about 20%O₂ in N₂ at temperatures between about 300 C to about 600 C for betweenabout 1 millisecond to about 60 minutes.

Second electrode layer, 906, is then formed above dielectric layer, 904.The second electrode layer may include a single layer or may includemultiple layers as discussed previously. In some embodiments, the secondelectrode layer is typically a metal such as ruthenium, platinum,titanium nitride, tantalum nitride, titanium-aluminum-nitride, tungsten,tungsten nitride, molybdenum, molybdenum nitride, vanadium nitride, orothers. In some embodiments, the conductive metal oxide portion of thesecond electrode layer is a conductive metal oxide. In some embodiments,the second electrode layer may include at least one of the conductivecompounds of molybdenum oxide, tungsten oxide, ruthenium oxide, iridiumoxide, chromium oxide, manganese oxide, or tin oxide. Specificconductive metal oxide materials of interest are the conductive metalcompounds of molybdenum oxide, ruthenium oxide, manganese oxide,tungsten oxide, and tin oxide. In some embodiments, the second electrodelayer includes a conductive base layer formed above the conductive metaloxide. In some embodiments, the conductive base layer includes one ofruthenium, platinum, titanium nitride, tantalum nitride,titanium-aluminum-nitride, tungsten, tungsten nitride, molybdenum,molybdenum nitride, or vanadium nitride. The conductive metal oxideportion of the second electrode is formed using a high temperature, lowpressure ALD process as discussed previously. Advantageously, theconductive metal oxide portion of the second electrode is molybdenumoxide. The second electrode is typically between about 5 nm and 50 nm inthickness. Typically, the capacitor stack would then be subjected to aPMA treatment in an oxidizing atmosphere, wherein the oxidizingatmosphere includes between 0% O₂ to 20% O₂ and at temperatures between300 C to 600 C for between 1 millisecond to 60 minutes. The PMAtreatment serves to crystallize the second electrode and to annealdefects and interface states that are formed at the dielectric/secondelectrode interface during the deposition. Those skilled in the art willunderstand that other layers may be included in the capacitor stack.

An example of a specific application of some embodiments is in thefabrication of capacitors used in the memory cells in DRAM devices, DRAMmemory cells effectively use a capacitor to store charge for a period oftime, with the charge being electronically “read” to determine whether alogical “one” or “zero” has been stored in the associated cell.Conventionally, a cell transistor is used to access the cell. The celltransistor is turned “on” in order to store data on each associatedcapacitor and is otherwise turned “off” to isolate the capacitor andpreserve its charge. More complex DRAM cell structures exist, but thisbasic DRAM structure will be used for illustrating the application ofthis disclosure to capacitor manufacturing and to DRAM manufacturing.FIG. 10 is used to illustrate one DRAM cell, 1020, manufactured using afirst electrode structure as discussed previously. The cell, 1020, isillustrated schematically to include two principle components, a cellcapacitor, 1000, and a cell transistor, 1002. The cell transistor isusually constituted by a MOS transistor having a gate, 1014, source,1010, and drain, 1012. The gate is usually connected to a word line andone of the source or drain is connected to a bit line. The cellcapacitor has a lower or storage electrode and an upper or plateelectrode. The storage electrode is connected to the other of the sourceor drain and the plate electrode is connected to a reference potentialconductor. The cell transistor is, when selected, turned “on” by anactive level of the word line to read or write data from or into thecell capacitor via the bit line.

As was described previously in connection with FIG. 9, the cellcapacitor, 1000, includes a first electrode layer, 1004, formed abovesubstrate, 1001. The first electrode layer, 1004, is connected to thesource or drain of the cell transistor, 1002. For illustrative purposes,the first electrode layer has been connected to the source, 1010, inthis example. For the purposes of illustration, first electrode layer,1004, will include a conductive metal oxide (i.e. conductive molybdenumoxide in this example) formed using a high temperature, low pressure ALDprocess as described previously. The first electrode layer may include asingle layer or may include multiple layers as discussed previously. Insome embodiments, the first electrode layer may include at least one ofthe conductive compounds of molybdenum oxide, tungsten oxide, rutheniumoxide, iridium oxide, chromium oxide, manganese oxide, or tin oxide.Specific conductive metal oxide materials of interest are the conductivemetal compounds of molybdenum oxide, ruthenium oxide, manganese oxide,tungsten oxide, and tin oxide. In some embodiments, the first electrodelayer includes a conductive base layer formed under the conductive metaloxide. In some embodiments, the conductive base layer includes one ofruthenium, platinum, titanium nitride, tantalum nitride,titanium-aluminum-nitride, tungsten, tungsten nitride, molybdenum,molybdenum nitride, or vanadium nitride. As discussed previously, firstelectrode layer, 1004, may be subjected to an anneal in a reducingatmosphere before the formation of the dielectric layer to crystallizethe conductive metal oxide and to reduce any oxygen-rich compounds thatmay have formed during the formation of the first electrode layer.Dielectric layer, 1006, is formed above the first electrode layer. Forthe purposes of illustration, dielectric layer, 1006, will berutile-phase titanium oxide. As discussed previously, the titanium oxidemay be doped. Typical dopants for titanium oxide include Al, Ce, Co, Er,Ga, Gd, Ge, Hf, In, La, Lu, Mg, Mn, Nd, Pr, Sc, Si, Sn, Sr, Y, Zr, orcombinations thereof. Typically, the dielectric layer is then subjectedto a PDA treatment. The second electrode layer, 1008, is then formedabove the dielectric layer. The second electrode layer may include asingle layer or may include multiple layers as discussed previously. Insome embodiments, the second electrode layer is typically a metal suchas ruthenium, platinum, titanium nitride, tantalum nitride,titanium-aluminum-nitride, tungsten, tungsten nitride, molybdenum,molybdenum nitride, vanadium nitride, or others. In some embodiments,the conductive metal oxide portion of the second electrode layer is aconductive metal oxide. In some embodiments, the second electrode layermay include at least one of the conductive compounds of molybdenumoxide, tungsten oxide, ruthenium oxide, iridium oxide, chromium oxide,manganese oxide, or tin oxide. Specific conductive metal oxide materialsof interest are the conductive metal compounds of molybdenum oxide,ruthenium oxide, manganese oxide, tungsten oxide, and tin oxide. In someembodiments, the second electrode layer includes a conductive base layerformed above the conductive metal oxide. In some embodiments, theconductive base layer includes one of ruthenium, platinum, titaniumnitride, tantalum nitride, titanium-aluminum-nitride, tungsten, tungstennitride, molybdenum, molybdenum nitride, or vanadium nitride. Theconductive metal oxide portion of the second electrode is formed using ahigh temperature, low pressure ALD process as discussed previously.Advantageously, the conductive metal oxide portion of the secondelectrode is molybdenum oxide. Typically, the capacitor stack would thenbe subjected to a PMA treatment in an oxidizing atmosphere, wherein theoxidizing atmosphere includes between 0% O₂ to 20% O₂ and attemperatures between 300 C to 600 C for between 1 millisecond to 60minutes. This completes the formation of the capacitor stack. Thoseskilled in the art will understand that other layers may be included inthe capacitor stack.

Although the foregoing examples have been described in some detail forpurposes of clarity of understanding, the invention is not limited tothe details provided. There are many alternative ways of implementingthe invention. The disclosed examples are illustrative and notrestrictive.

What is claimed:
 1. A method for forming a capacitor stack, the methodcomprising: forming a first electrode layer above a substrate; forming adielectric layer above the first electrode layer; and forming a secondelectrode layer above the dielectric layer; wherein the first electrodelayer comprises molybdenum oxide having a distorted rutile structure,the dielectric layer comprising a dielectric material, the molybdenumoxide of the first electrode layer directly interfacing the dielectricmaterial of the dielectric layer and operating as a template for formingthe dielectric material in a rutile phase while forming the dielectriclayer, the first electrode layer formed using a first ALD process at atemperature between 280 C and 360 C and at a pressure between 0.10 Torrand 1.00 Torr.
 2. The method of claim 1, wherein the first electrodelayer further comprises one of ruthenium, platinum, titanium nitride,tantalum nitride, titanium-aluminumnitride, tungsten, tungsten nitride,molybdenum, molybdenum nitride, or vanadium nitride.
 3. The method ofclaim 1, wherein the dielectric material comprises one of aluminumoxide, barium-strontium-titanate (BST), hafnium oxide, hafnium silicate,niobium oxide, lead-zirconium-titanate (PZT), a bilayer of silicon oxideand silicon nitride, silicon oxy-nitride, strontium-titanate (STO),tantalum oxide, titanium oxide, zirconium oxide or doped versions of thesame.
 4. The method of claim 3, wherein the dielectric materialcomprises titanium oxide.
 5. The method of claim 4, wherein thedielectric material further comprises a dopant, the dopant comprising atleast one of Al, Ce, Co, Er, Ga, Gd, Ge, Hf, In, La, Lu, Mg, Mn, Nd, Pr,Sc, Si, Sn, Sr, Y, or Zr.
 6. The method of claim 1, wherein the secondelectrode layer is formed using a second ALD process at a temperaturebetween 280 C and 360 C and at a pressure between 0.10 Torr and 1.00Torr.
 7. The method of claim 1, wherein the first ALD process isperformed at a temperature of substantially 320 C and at a pressure ofsubstantially 0.25 Torr.
 8. The method of claim 1 wherein the firstelectrode layer is annealed before the forming of the dielectric layer.9. The method of claim 8, wherein annealing of the first electrode layeris performed in a reducing atmosphere comprising between about 0% andabout 10% H₂ in N₂ or one or more other inert gases and at a temperatureof between about 400 C and about 650 C for between about 1 millisecondand about 60 minutes.
 10. The method of claim 1 wherein the firstelectrode layer and the dielectric layer are annealed before the formingof the second electrode layer.
 11. The method of claim 10, whereinannealing of the second electrode layer is performed in an oxidizingatmosphere at a temperature of between 300 C to 600 C for between 1millisecond to 60 minutes.
 12. The method of claim 11 wherein theoxidizing atmosphere comprises between 0% O₂ to 20% O₂ in N₂.
 13. Themethod of claim 1, wherein the second electrode layer comprises one ofruthenium, platinum, titanium nitride, tantalum nitride,titanium-aluminum-nitride, tungsten, tungsten nitride, molybdenum,molybdenum nitride, or vanadium nitride.
 14. The method of claim 13,wherein the second electrode layer comprises titanium nitride.
 15. Themethod of claim 1, wherein the second electrode layer comprises one ofmolybdenum oxide, tungsten oxide, ruthenium oxide, iridium oxide,chromium oxide, manganese oxide, or tin oxide.
 16. The method of claim15, wherein the second electrode layer comprises molybdenum oxide. 17.The method of claim 1, further comprising annealing the first electrodelayer, the dielectric layer, and the second electrode layer in anoxidizing environment after forming of the second electrode layer. 18.The method of claim 17 wherein the oxidizing environment comprisesbetween 0% O₂ to 20% O₂ and at temperatures between 300 C to 600 C forbetween 1 millisecond to 60 minutes.